Process of treating bituminous substances



Patented Jan. 19, 1926.

UNITED STATES PATENT OFFICE.

GEORGE W. ACHESON, OF CALDWELL, NEW JERSEY.

PROCESS OF TREATING BITUMINOUS SUBSTANCES.

No Drawing.

nous Substances, of which the following is a specification.

This invention relates to the refining of" l'lydrocarbons, and more particularly to the desulfurizing of crude petroleum oils and bituminous products in general, including mineral oils and waxes, shale oils and waxes, and similar substances. My novel process depends in its preferred embodiment, as applied to sulfur-containing oils, upon the conjoint action of an acid reagent and a solid adsorbent material, the latter comprising a solid body which has been reprecipitated from the 'deflocculated or colloidal state. My preferred solid adsorbent comprises clay, reprecipitated from the colloidal or deflocculated state, and is preferably prepared in the manner disclosed in the prior patents to E. G. Acheson, Numbers 1,456,111 and 1,456,112, patented May 22, 1923. As more fully explained in the aforesaid Patent 1,456,112, the term defloeculation is employed herein to indicate a subdivision of matter brought about through the agency of certain organic bodies known in this art as deflocculating agents. WVhen such delocculating agents are incorporated with the body to be defloccnlated, the latter in presence of a sufficiently restricted body of water or other liquid, and the resulting heavy paste is subjected to prolonged mechanical working, the component particles, or a portion of them, undergo deflocculation with the result that they are subdivided into extremely minute masses, which in some cases at least are now believed to be of molecular dimensions. Such deflocculated particles are beyond the limits of visibility under ordinary microscopic observation, but appear under the ultra microscope as brilliant points in intense vibratory movement. Processes of deflocculation and deflocculating agents for use in connection therewith are disclosed in. many prior patents to E. G. Acheson, among which may be mentioned U. S. 1,223,350, of April 24, 1917, as disclosing a preferred mechanical method of effecting the deflocculation; U. S. 1,253,556, of January 15, 1918, and 1,345,305, of June Application filed August 14, 1924. Serial- No. 732,112.

I 29, 1920, as disclosing preferred deflocculating agents; and U. S. 1,345,306 of June 29, 1920, as disclosing the preferred moisture relations, in the deflocculating process. However the deflocculation may be accomplished, the deflocculated or colloidal particles may be precipitated from their solution or suspension by the addition of small proportions of electrolytes such as hydrochloric acid, alum or the like. The particles are thereby precipitated in the form of fragile and porous aggregates, which present enormous surfaces relative to their weight.

In one particular embodiment of my invention I proceed as follows, it being understood that my invention is not restricted to the specific materials, proportions, or manipulations described by way of example; for as will readily be understood these conditions must be varied according to the particular raw material to be treated and the object sought to be attained.

A sulfur-containing crude oil from one of the larger pipe lines was thoroughly agitated at summer temperature F.) with about six percent by weight of clay, prepared as described above by precipitation from the deflocculated suspension and thereafter dried and calcined at low red heat, short of the sintering temperature. To the resulting homogeneous mixture 66 B. sulfuric was slowly added with constant stirring, up to about four percent by weight of the oil. Thereafter a further smaller proportion of the precipitated clay was stirred in, amounting to about two percent by weight of the oil. The precipitate was permitted to settle and the oil separated by decantation and filtration. The sulfur-content of the oil was found to be largely reduced, and the oil was so nearly neutral as not to require in this particular case any after treatment with alkali. The clay precipitate was heavily charged with sulfur compounds. The clay may be introduced into the oil either as fine powder, or as fragments up to pea-size or larger, the latter practice having the great advantage of permitting the quick separation of the oil from the clarifying agent.

I do not wish to limit my invention by reference to any theory regarding the chemical or physical reactions which may take place; but I now believe that the function of the solid adsorbent material in the above example is essentially physical, taking up by adsorption the sulfur compounds contained in the oil or resulting from the acid treatment. If such is the case, it may be anticipated that any solid material which is susceptible of defiocculation and reflocculation will serve the same purpose, as for example deflocculated and reprecipitated carbon black, fullers earth and siliceous materials. and this is confirmed by the data at hand. Similarly any reagent, as for example chlorinc, which is capable of breaking down the sulfur compounds, or preparing them otherwise to be adsorbed by the solid material performs the functions of the sulfuric acid and is to be re arded as an equivalent thereof for the purposes of this invention. Nor do I wish to be limited to the use of an acid or equivalent reagent in conjunction with the solid adsorbent, for I have observed that in the case of certain oils a material and substantial elimination of sulfur may be accomplished by the solid adsorbent alone without the use of acid; and in case of nonsulfur-bearing oils the use of acid may be omitted. Similarly I do not desire to be restricted to the addition of the reagents in the order described above, for a material and substantial improvement in the oil may be efiected by merely stirring the solid adsorbent into an acid-treated oil. I believe myself to be the first to have observed the puritying and refining action upon mineral oils or other bituminous substances, whether sulfurbearing or not, of solid adsorbents which have been prepared by precipitation from the deflocculated or colloidal state, and I desire to claim the same broadly.

The term bitumen is employed herein in ts broad sense to include hydrocarbon bodies in general, and especially mineral oils, waxes, etc., and products derived therefrom by distillation or otherwise.

The term refiocculated solid adsorbent material is used herein to designate any solid material which has been subjected to the process of deflocculation and reprecipitated from the resulting suspension or colloidal solution. It will be understood that this precipitate may consist wholly of reflocculated material, or of the same in admixture with particles of coarser order.

I claim:

1. In a process of treating bituminous substances, the step comprising reacting thereon With a reflocculated solid adsorbent material.

2. In a process of treating sulfur-containing bituminous substances, the step comprising reacting thereon with a refiocculated solid adsorbent material and a reagent capable of aiding the adsorption of sulfur thereby.

3. In a process of treating sulfur-containing bituminous substances, the step comprising reacting thereon with a reflocculated solid adsorbent material and an acid re agent.

i. The process of treating sulfur-containing oils comprising contacting the oil with a reflocculated solid adsorbent material, adding an acid reagent, and thereafter contacting the oil with additional reflocculated solid adsorbent material.

5. In a process of treating bituminous substances, the step comprising reacting thereon with reflocculated clay.

6. In a process of treating sulfur-containing bituminous substances, the step comprising reacting thereon with reflocculated clay and a reagent capable of aiding the adsorption of sulfur thereby.

7. In a process of treating sulfur-containing bituminous substances, the step compris ing reacting thereon with reflocculated clay and an acid reagent.

8. The process of treating sulfur-containing oils comprising contacting the oil with reflocculated clay, addin an acid reagent, and thereafter contacting the oil with additional reflocculated solid adsorbent material.

In testimony whereof, I afiix my signature.

GEORGE IV. ACHESON. 

